Composition for heat-recoverable foam tubing

ABSTRACT

Provided is a melt composition for a heat shrinkable foam structure that includes at least one base polymer and a blowing agent made from at least one heat-activated chemical compound encapsulated by a plurality of polymeric shells. The melt composition may also include a crosslinking promoter or other additives. Also provided is a method for making a heat-shrinkable polymer foam tubing. A melt composition containing at least one base polymer material having a melt temperature and a blowing agent having an activation temperature is provided. The melt composition is mixed at an elevated temperature. The melt composition is then extruded through a die at a high temperature. The extruded foam tube is then processed, often heat-processed. Additionally provided is a heat shrinkable foamed polymer tube containing an inner layer and an outer layer of an extruded foamed polymer tube, where each layer is made from at least one base polymer and a blowing agent and the blowing agent includes a heat-activated chemical compound encapsulated in a plurality of polymer shells.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present application relates to a polymeric foam tubing which can beheat-recovered, e.g. heat-shrunk. More specifically, it relates to anextruded polymeric foam tubing including a dispersed, encapsulatedblowing agent.

2. Introduction to the Invention

Insulation, padding or a protective covering is often required for avariety of substrates, such as metallic wires, rods, pipes, or otherelongated irregular shapes, such as handles and grips, in a broad rangeof applications, from tools and appliances to clothing. A foamed polymercoating is an effective and inexpensive method of providing suchinsulation or padding. In particular, a tubular foam structure can beextruded, and made into a heat shrinkable tubing. When the substrate isinserted into the foam tube and then the tube is heated above themelting point of the polymer used in the polymer composition of thetube, the heat shrinkable polymer foam tubing will recover snugly overthe substrate.

Extrusion is a continuous molding process often used with polymermaterials. In extrusion, a polymer material is continuously heated andmechanically worked into a homogeneous charge of viscous fluid in themelt phase. Alternatively, the polymer may be introduced into theextrusion device already in a melt phase. The heated charge is thenforced through an open-ended die. The polymer is extruded from the diein the general shape of the die; often, it is an annular shape. Theextruded melt is then solidified by air cooling or water quenching theextruded material. To make a heat-recoverable article, the solidifiedmaterial usually is crosslinked, and then mechanically expanded.Applying heat to the expanded article causes it to recover, usually byshrinking, to approximately its original, unexpanded shape.

When a foamed extrudate is desired, the polymer melt is often mixed witha blowing agent. Chemical blowing agents typically are in the form ofheat-activated fine powders, such as sodium bicarbonate orazodicarbonamide. When the polymer material containing the blowing agentpowder is heated and melted, the bulk of the powder decomposes and formspockets or balloons of gas within the structure of the polymer melt. Thegas immediately dissolves into the polymer melt, and mainly staysdissolved within the melt due to the prevailing high pressure in theextruder at extrusion process conditions. However, in the conventionaltube extrusion process of forming a tube of foamed polymer material,some of the dissolved gas is released into the inner cavity of theextruded polymer foam tube as the molten polymeric material exits thedie. This can lead to deformities in the shape and dimensions of thefinal product.

Alternatively, physical blowing agents have been introduced into thepolymer melt late in the extrusion process, i.e. after heating thepolymer, but before the final pumping of the polymer melt through theextrusion die. Such a process still suffers from the same disadvantagesas the previously described conventional process, and variations inpolymer foam tube shape and dimensions are still present at unacceptablelevels. Further, the foam cell size in the finished product has pooruniformity, which may adversely impact the ability of the tubing toexpand in diameter following a crosslinking step.

Accordingly, there is an existing need for a composition for a polymermelt for extrusion to be used in tubing that will create a foamedpolymeric material capable of being made into a useful heat shrinkablefoamed structure, preferably in a continuous process, such as tubeextrusion or parison blow-molding process, but not allow the gases toescape and deform the tubular structure.

BRIEF SUMMARY OF THE INVENTION

According to an embodiment of the present invention, there is provided amelt composition for a heat shrinkable foam structure. The compositioncomprises at least one base polymer and a blowing agent. The blowingagent itself comprises at least one heat-activated chemical compoundwith a polymeric shell encapsulating the heat-activated chemicalcompound.

According to another embodiment of the present invention, there isprovided a melt composition for a heat-shrinkable foam structure. Thecomposition comprises about 80 to about 99.9% by weight of anethylene/vinyl acetate copolymer base polymer, about 0.1 to about 10% byweight of a blowing agent, and, optionally, about 0 to about 19.9% byweight of an optional filler.

According to yet another embodiment of the present invention, there isprovided a method for making a heat-shrinkable polymer foam tubing. Amelt composition is first provided, which comprises at least one basepolymer material having a melt temperature and a blowing agent having anactivation temperature. The melt composition is mixed at an elevatedtemperature. The melt composition is then extruded through a die at ahigh temperature. The extruded foam tube is then post processed.

According to still another embodiment of the present invention, there isprovided a heat shrinkable foamed polymer tube comprising at least aninner layer and an outer layer of an extruded foamed polymer tube. Eachlayer is made from at least one base polymer and a blowing agent, wherethe blowing agent comprises a heat-activated chemical compoundencapsulated in a polymer shell.

Other aspects of the present invention will become apparent inconnection with the following description of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of the foamed polymer tube of an embodimentof the present invention having an inner surface and an outer surface;and

FIG. 2 is a perspective view of the foamed polymer tube of an embodimentof the present invention having an inner and outer layer, with anintermediate layer positioned between the two layers.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

A composition for a foamable polymer according to the inventioncomprises at least a base polymer composition and a blowing agent. Inaddition, the composition (also referred to herein as a meltcomposition) may include optional fillers, e.g., antioxidants,crosslinking promoters, heat stabilizers, colorants, flame retardants,and the like.

The base polymer material of the composition is chosen such that it willmelt easily, withstand the heat and pressure of extrusion withoutdegrading, and mix homogeneously with the blowing agent. A thermoplasticpolymer fulfills all requirements for a base polymer. Preferred basepolymer compositions include, without limitation, polyethylenes,including very low density polyethylene, low density polyethylene,medium density polyethylene, high density polyethylene, and metallocenepolymerized ethylene; C4-C10 olefin-containing ethylene copolymers;copolymers and terpolymers of polyethylene with vinyl acetate, alkylacetate, acrylic acid, maleic anhydride or carboxylic acid;polypropylene; ethylene propylene diene rubbers (EPDM); styrenebutadiene rubbers; rubber blends with polyolefins; polyurethanes;polyamides; polyesters; polysiloxanes; fluoropolymers; otherthermoplastic polymers; and mixtures of two or more of these. It isoften desirable to mix a polymer having a relatively high level ofcrystallinity with a polymer having a relatively low level ofcrystallinity in order to achieve specific heat-recoverable properties.One preferred base polymer may be obtained from DuPont, anethylene/vinyl acetate copolymer (EVA) sold under the tradename Elvax™460.

The selection of a base polymer material is dependent on the end use ofthe product, and any other material or process concerns, as is known tothose in the art. For example, a base polymer for use in a tube able tobe easily installed at a low heat-shrink temperature and having acomfortable grip, such as high vinyl acetate content (i.e. at least 15%by weight) EVA polymer or an EVA-EPDM polymer blend, might be used tocreate a guard on an outdoor appliance such as a lawmnower, while a basepolymer able to withstand attack by corrosive chemicals, such as apolyvinylidene fluoride/hexafluoropropylene copolymer, may be used tocreate insulation for a pipe.

The base polymer is generally present at about 80% by weight to about99.9% by weight of the melt composition, preferably about 90% by weightto about 99.9% by weight of the melt composition.

The invention utilizes a blowing agent in the form of a plurality ofpolymeric shells encapsulating a heat-activated chemical compound. Thesecapsules are often called microballoons. The chemical compound chosen ispreferably a liquid at room temperature, and has a relatively lowboiling point, i.e. less than 50° C. The specific chemical compound andpolymeric shell materials are chosen such that the polymeric shellsremain intact throughout the rigors of extrusion; more specifically, apolymer shell material is chosen such that the shell will not degrade ormelt under the heat and pressure used in the mixing process, and willnot rupture during the applied forces of the extrusion process.

The microballoons also have an activation temperature at which theencapsulated liquid begins to boil and turn into a gas. At thisactivation temperature, the polymer shells are soft enough to begin toexpand to allow for the increase in volume as the chemical compoundenters a gaseous phase while still effectively encapsulating thechemical compound. This expansion of the microballoons forms the voidsin the base polymer in order to create a foamed material. Generally theactivation temperature comprises a range in order to accommodatedifferences in microballoon size in a particular batch of product. Inaddition, encapsulated blowing agents are often defined in terms of aminimum expansion temperature (or temperature range), i.e. thetemperature at which the encapsulant begins to expand, and a maximumexpansion temperature (or temperature range), i.e. the temperature atwhich the encapsulant has completed expansion. The activationtemperature is generally somewhat lower than the maximum expansiontemperature.

The polymeric shell can comprise, without limitation, polymers andcopolymers of vinyl chloride, vinylidene chloride, acrylonitrile,methacrylonitrile, styrene, or combinations thereof. Preferably, thepolymeric shell encapsulates a hydrocarbon-based liquid such asisopentane or isobutane.

In a preferred embodiment of the present invention, the unexpandedpolymer shells preferably have a diameter ranging from about 3 μm toabout 60 μm, more preferably from about 6 μm to about 40 μm. The densityof the unexpanded encapsulated blowing agent is generally less than 25kg/m³. The unexpanded encapsulated blowing agent is preferably used at aweight percent of between about 0.1% and about 10% of the meltcomposition, more preferably between about 1% and about 7% of the meltcomposition, and most preferably between about 2.5% and about 6% of themelt composition, although the amount of blowing agent used is afunction of the type of polymer, the type of blowing agent, and thepresence of optional fillers.

One preferred encapsulated blowing agent is Expancel™ polymericmicroballoons, available from Expancel, Inc. In general, suchmicroballoons have an unexpanded diameter between about 6 μm and about40 μm, and an expanded diameter between about 20 μm and about 150 μm.More preferably, the encapsulated heat-activated blowing agent isExpancel™ 091-DU-80 or Expancel™ 092-DU-120, both of which havepolymeric shells comprising copolymers of acrylonitrile andmethacrylonitrile, and both of which encapsulate isopentane.

Selection of a blowing agent is dependent in part on the base polymerchosen for the application and the processing temperatures used in theextrusion process. There are two important temperature zones in theextrusion or blow-molding process—the mixing or melt blendingtemperature zone, where melting of the base polymer occurs, and theextrusion die temperature zone. The mixing temperature zone is selectedto be at a higher temperature than the melting temperature of the basepolymer. The melting temperature is defined as the peak of the endothermof a differential scanning calorimeter (DSC) trace. When the meltcomposition comprises more than one polymer and more than one peak ispresent on the DSC trace, the melting temperature is defined as thehighest temperature peak.

In order to create a uniform, stable foam, however, it is preferablethat the blowing agent microballoons do not begin to expand until, orjust slightly before, the time when the polymer mixture is extrudedthrough the die, and not prematurely. Preferably the blowing agent willbe chosen such that its activation temperature is higher than that inthe mixing temperature zone, but lower than that in the extrusion dietemperature zone. It is therefore preferable to choose a blowing agentwith a minimum expansion temperature above the melting temperature ofthe base polymer, so that expansion does not occur while the basepolymer material is melting. More preferably, the chosen blowing agenthas a minimum expansion temperature higher than the desired mixingtemperature of the melting step of the extrusion process.

In order to produce a heat-recoverable tube, the polymer material isoften crosslinked. Crosslinking gives the polymer a “memory” of itscurrent shape, and gives the finished polymer tube the ability to shrinkor otherwise change shape upon heating. Crosslinking also increases thestructural rigidity of the foamed polymer and assures that the foam willnot decompress, or “go flat” when expanded or heat-shrunk. Crosslinkingmay be achieved by radiation or chemical means, and the polymer mixturemay comprise crosslinking agents or promoters to increase the amount ofcrosslinking between discrete polymer chains. There are two generaltypes of crosslinking promoters—chemical crosslinking promoters andradiation crosslinking promoters. Either or both of these types ofcrosslinking promoters may be used, although for some preferredembodiments it is preferred that only a radiation crosslinking promoteris used.

A radiation crosslinking promoter acts as a catalyst to polymercrosslinking when exposed to radiation, such as from a high energyelectron beam. The radiation crosslinking promoter may be chosen fromamong those conventionally used to promote crosslinking of polymers,including triallyl cyanurate (TAC), triallyl isocyanurate (TAIC),triallyl trimellitate, triallyl trimesate, tetrallyl pyromellitate, thedually ester of 1,1,3,-trimethyl-5-carboxy-3-(4-carboxyphenyl)indene,trimethylolpropane trimellitate (TMPTM), pentaerythritoltrimethacrylate, tri(2-acryloxyethyl) isocyanurate,tri(2-methacryloxyethyl) trimellitate, and the like and combinationsthereof. A particularly preferred radiation crosslinking promoter isTMPTM commercially available as Sartomer™ SR 350 from Sartomer Company.

Flame retardants may also be added in an amount as will provideeffective flame retardancy for the foamable tube. Suitable flameretardants generally comprise polybrominated aromatics, such asdecabromobiphenyl, in combination with inorganic materials, such asantimony trioxide. Other fillers such as antioxidants, adhesionpromoters, UV screeners, plasticizers, colorants, heat stabilizers, andother additives may also be employed in conventional amounts. Suchadditives may be chosen based on the final end use of the product, as isknown to those of skill in the art.

The quantity of optional fillers (which in this specification includesboth crosslinking promoters and flame retardants, as well as the otherfillers and additives referred to above) present in the melt compositionis dependent on the type and quantity of base polymer and encapsulatedblowing agent, as well as the desired physical properties. In general,the quantity of optional fillers is at most about 35% by weight of themelt composition, preferably at most about 20% by weight of the meltcomposition, particularly at most about 10% by weight of the meltcomposition, e.g. about 0 to about 19.9% by weight of the meltcomposition.

The extrusion process for a foamable polymer according to the presentinvention is similar to that known to those of skill in the art. Thebase polymer is first mixed with the blowing agent and other foamablepolymer composition elements. Mixing is performed by any method known tothose of skill in the art; preferably, mixing occurs by a Banbury typeof a mixer. A twin-screw mixing device may also be successfullyemployed. Mixing occurs at an elevated temperature selected to be highenough that the base polymer will melt during mixing, but not highenough to activate the other components of the polymer mix, such as theblowing agent or any crosslinking promoter, if present. Preferably,therefore, the mixing step takes place at a temperature higher than themelt temperature of the selected base polymer, but below the minimumactivation temperatures of the blowing agent.

The mixed polymer blend, in a melt state, is then extruded through adie, as is known in the art. For the present application, the die ispreferably an annular or ring-shaped die; however, the die may be of anyshape known in the art and preferred for a chosen end result. Thetemperature of the polymer blend after melting and mixing but beforeextrusion can be independently set from the temperature at the time andpoint of extrusion. Preferably, the post-mixing, pre-extrusiontemperature is set at a temperature equal to or higher than that ofmixing, but less than the activation temperatures of the components inthe polymer blend. More preferably, the post-mixing, pre-extrusiontemperature is set at a temperature higher than that of mixing, but lessthan the minimum activation temperatures of the components in thepolymer blend. The temperature at the point of extrusion is preferablyset well above the minimum activation temperature of at least theblowing agent, i.e. at least 10° C. above. By waiting until just beforeextrusion to reach a temperature that activates the blowing agent, ithas been found that a more stable, uniform foam is created. At the timeof activation, the liquid inside the polymer capsules of the blowingagent changes phase into a gaseous state, and the capsule expands tocreate a gas pocket. The melt composition is thereby preferably formedinto the desired shape, e.g. by extrusion, and foamed at approximatelythe same time. The melt composition leaves the extruding process as afoamed polymer tube that has not yet been expanded in size.

Once the tube has undergone extrusion and foaming, the blowing agentmicroballoons are in a fully expanded state, and the base polymer is ina melt, i.e. a highly viscous liquid-like state. As the extruded foamtube begins to cool just after extrusion, the polymer begins to solidifyaround the expanded microballoons. The microballoons are then frozen inan expanded state, creating the voids in the foam.

After extrusion, the foamed polymer tube undergoes post processing,generally including one step that involves exposure to heat. In apreferred first step, the foamed polymer tube can be cross-linked.Depending on the type of crosslinking process used, the tube isirradiated or heated to the proper temperature to activate the chemicalcrosslinking promoter. Irradiation occurs by any method known in theart, such as high energy electron beam irradiation. The purpose ofcrosslinking the polymer strands in the foam is to give the tube a“memory” of the current tube shape and diameter as well as structuralstability above the melting point of the base resin.

Next, the tube is expanded by any means known in the art, such asshaping on a mandrel or use of a vacuum apparatus. Preferably, the tubeis expanded by the process of pressure differential expansion. Inpressure differential expansion, the foamed polymer tube is first heatedto a temperature sufficient to melt the crystalline polymer regions ofthe foamed polymer tube. The heated tube is then subjected to a pressuredifferential along the tube wall while maintaining the elevatedtemperature. The pressure differential is preferably such that the airpressure within the tube is greater than that outside the tube. Methodsfor imposing this air pressure differential are known to those of skillin the art. The air pressure differential expands the diameter of thetube. The pressure differential is directly related to the finishedexpanded diameter of the foamed polymer tube; by adjusting the pressuredifferential and/or other variables, e.g. the sizing die internaldiameter, a desired expanded diameter can be attained.

After the tube has been expanded, and while the pressure differential ismaintained, the foamed polymer tube is rapidly cooled if it has beenheated during expansion. This rapid cooling freezes the physical polymerfoam positions in place in the expanded state. The cooling also servesto solidify the foamed polymer tube. After cooling, the foamed polymertube will remain in its expanded state until heated again. Once theexpanded tube is reheated or “recovered”, it will contract back toapproximately its original size.

In a preferred embodiment, a multi-layer approach may be used whereinthe polymer tube is made from a first, inner layer and a second, outerlayer, both made by the process disclosed above. The two layers may beco-extruded. In such an embodiment, the inner and outer layer materialsmay comprise the same or different base polymer and the same ordifferent blowing agent. The inner and outer layers may havesignificantly different mechanical properties, or have been foamed todifferent levels of void content, so as to tailor the overallperformance of the product to specific end user needs. For example, anexcellent balance of softness, tactile feel, vibration dampeningcharacteristics, mechanical robustness and heat shrink performanceattributes is achieved when the inner layer is made from asemicrystalline base polymer material and is foamed to a lower level ofvoid content, while an outer layer is made out of a softer, amorphous orelastomeric, base polymer material blend and is foamed to a higher levelof void content. (The void content can be determined by comparing thespecific gravity of the melt composition in its unexpanded solid statewith the specific gravity of the composition after it has beenexpanded.) Similarly, a tackifying filler, such as novolak resins,partially polymerized resins, tall oil resin esters, or low molecularweight aromatic thermoplastic resins, may be added to the inner layer. Atackifier increases the adhesive quality of the foam surface, andenhances its adherence to the substrate over which the heat-shrinkablepolymer foam would be installed. For many applications, theheat-recoverability performance is enhanced when one of the layerscomprises a base polymer having a significant level of crystallinity,e.g. at least 10%.

Additional layers may be present in the polymer tube. For example, anon-foamed adhesive layer, preferably added after the foaming of thetube, may be present on the inner surface of the tube in order toenhance bonding to a substrate. Alternatively, an intermediate layer,either foamed or unfoamed, may be present to provide structural support.

The invention is illustrated by the drawings in which FIG. 1 is aperspective view of foamed tube 1 of the invention in which meltcomposition 3 in the form of a tube has inner surface 5 and outersurface 7.

FIG. 2 is a perspective view of another foamed tube 1 of the invention.In this embodiment, intermediate layer 13 is positioned between innerlayer 11 and outer layer 15.

EXAMPLE

An exemplary formulation for the foamable composition using anencapsulated blowing agent is listed below in Table 1. TABLE 1 ExemplaryFoamable Polymer Tube Composition Ingredient Ingredient DescriptionProduct Supplier Weight Base Resin (EVA) Elvax ™ 460 Du Pont 90.5Encapsulated Expancel ™ 092 Expancel Inc. 3.0 Blowing Agent DU-120Radiation TMPTM Sartomer 2.0 Crosslinking Promoter Antioxidant Irganox ™1010 Ciba Specialty 2.0 Chemicals Heat Stabilizer Cyanox ™ 1212 CytecIndustries 1.0 Colorant (TiO₂) TiPure ™ 101 DuPont 1.0 Metal DeactivatorIrganox ™ 1024 Ciba Specialty 0.5 Chemicals TOTAL 100.0

According to product literature from the supplier, the selected blowingagent, Expancel™ 092 DU-120, had a particle size of 28-38 μm (based onweight average diameter), a minimum expansion temperature of 116-126°C., a maximum expansion temperature of 190-202° C., and a density ofless than 14 kg/m³ (based on thermomechanical analysis).

In preparing the exemplary polymer mix for extrusion, the twin-screwmixing mechanism was fitted with a three hole stranding die, with adiameter of about 3.2 mm (0.125 inch). Melting and mixing was carriedout between about 95° C. and about 110° C. at a feed rate of about 6.8kg/hr (15 pounds/hour) while the screws were turning at about 72revolutions/minute. No foaming was observed in the extruded strands whenexamined under a 30× microscope.

The compound was then pelletized, and extruded through a 51 mm (2 inch),24:1 L/D single screw extruder using standard commercially availabletooling. The extrusion process parameters used in this embodiment arelisted below in Table 2. Care was exercised to expand the microballoonsof the blowing agent by heating them above their minimum expansiontemperature in the final stages of their travel through the extruder.This was accomplished by raising the temperatures of the extrusionbarrel and crosshead containing the die to approximately, but not above,the maximum recommended expansion temperature of the blowing agent. Asindicated above, the maximum recommended expansion temperature for theblowing agent in the present exemplary embodiment is between about 190°C. and about 202° C. TABLE 2 Extrusion Process Parameters ProcessParameter Value Extruder Type/Barrel Davis Standard/51 mm (2.0 inch)Diameter Crosshead Type Davis Standard Screw Design low compressionratio screw Extrusion die inner diameter ×  9.7 mm (0.38 inch) × 25.4 mm(1.0 inch) land length. Extrusion tip outer diameter × 12.7 mm (0.5inch) × 27.9 mm (1.1 inch) land length Water Temperature in cooling 24°C. (75° F.) trough Vacuum 27.2 mm (1.07 inch) Hg Trough - Die Distance63.5 mm (2.5 inch) Extruder Screw Speed 16.9 rpm Drive Motor  5.3 AExtrusion Line Speed  7.6 m/min (25 feet/minute) Temperatures Degrees °F. Degrees ° C. Mixing Temperature 200  93 Extrusion Temperature 360 182

The extruded foam tubing, having maintained the internal diameter of thedie of about 9.7 mm (0.380 inch), next went through an expansionprocess. The extruded foam tube was first irradiated with about 6.1 Mradusing a 1.5 MeV electron beam to obtain a crosslinked polymer network inthe base resin.

The foamable tubing was then expanded by employing a pressuredifferential between the inside and outside surfaces of the tubing. Inthe present exemplary embodiment, the pre-expansion heating took placeat a temperature of about 130° C. Next, a pressure differential wasimparted across the tubing wall to expand the tubing to an internaldiameter of about 20 mm (0.8 inch). While subjected to the differentialpressure, the tubing was passed through a cooling zone at a velocity ofabout 7.6 m/minute (25 feet/minute). Further parameters used in theexpansion process of the exemplary embodiment are listed below in Table3. TABLE 3 Expansion Details Glycerin Bath Temperature  107° C. (225°F.) Tank Plug Die Type 12.1 mm (0.475 inch) Tank Pressure 72.4 kPa (10.5psi) Tube Pressure 89.6 kPa (13 psi) Line Speed 9.93 m/min (32.6 ft/min)Tank to Sizing Die Gap Setting 2.54 mm (0.100 inch)

Table 4 below gives the detailed mechanical characteristics of afinished product made by this exemplary procedure. Upon heating of theexpanded foamable polymer tube, the tube recovered back to approximatelythe original extruded inside diameter. TABLE 4 Product CharacteristicsExpanded Inside Diameter 18.3 ± 0.5 mm (0.720 ± 0.020 inch) ExpandedWall Thickness 0.64-0.74 mm (0.025-0.029 inch) Extruded Inside Diameter8.26 mm (0.325 inch) Extruded Wall Thickness 1.60-1.75 mm (0.063-0.069inch) Recovered Inside Diameter 9.1 mm (0.357 inch) (150° C. for 3 min)Recovered Wall Thickness 1.78-1.96 mm (0.070-0.077 inch) (150° C. for 3min) Longitudinal Change in length −4.0%    (150° C. for 3 min) AsExtruded Specific Gravity 0.42 g/cm³ As Extruded Percent Air Voids 56%As Expanded Specific Gravity 0.47 g/cm³ As Expanded Percent Air Voids52% As Recovered Specific Gravity 0.35 g/cm³ As Recovered Percent AirVoids 66%

It is therefore intended that the foregoing detailed description beregarded as illustrative rather than limiting, and that it be understoodthat it is the following claims, including all equivalents, that areintended to define the spirit and scope of this invention.

1. A melt composition for a heat shrinkable foam structure, saidcomposition comprising: (1) at least one base polymer; and (2) a blowingagent, said blowing agent comprising: (a) a plurality of polymericshells; and (b) at least one heat-activated chemical compound, saidheat-activated chemical compound encapsulated in said polymeric shells.2. The melt composition of claim 1, wherein said at least one basepolymer comprises a thermoplastic.
 3. The melt composition of claim 2,wherein the thermoplastic is selected from the group consisting of: verylow density polyethylene, low density polyethylene, medium densitypolyethylene, high density polyethylene, metallocene polymerizedethylene, C4-C10 olefin-containing ethylene copolymers, copolymers andterpolymers of poly ethylene with vinyl acetate, alkyl acetate, maleicanhydride, or carboxylic acid, polypropylene, ethylene propylene dienerubbers, styrene butadiene rubbers, rubber blends with polyolefins,polyurethanes, polyamides, polyesters, polysiloxanes, andfluoropolymers, and mixtures thereof.
 4. The melt composition of claim1, wherein said heat-activated chemical compound is selected from thegroup consisting of isopentane and isobutane.
 5. The melt composition ofclaim 1, wherein said polymeric shells comprise a copolymer ofacrylonitrile and methacrylonitrile.
 6. The melt composition of claim 1,further comprising a crosslinking promoter.
 7. The melt composition ofclaim 6, wherein said crosslinking promoter comprises a radiationcrosslinking promoter.
 8. The melt composition of claim 7, wherein saidradiation crosslinking promoter comprises trimethylolpropanetrimellitate.
 9. The melt composition of claim 1, further comprising atleast one additive, said additive selected from the group consisting ofan antioxidant, a heat stabilizer, a colorant, and a metal deactivator.10. The melt composition of claim 1, wherein said blowing agent ispresent in said melt composition at a weight percentage of about 0.1% toabout 10%.
 11. The melt composition of claim 10, wherein said blowingagent is present in said melt composition at a weight percentage ofabout 1% to about 7%.
 12. The melt composition of claim 11, wherein saidblowing agent is present in said melt composition at a weight percentageof about 2.5% to about 6%.
 13. The melt composition of claim 1, whereinsaid polymeric shells of said blowing agent have a diameter of about 3μm to about 60 μm.
 14. The melt composition of claim 13, wherein saidpolymeric shells of said blowing agent have a diameter of about 6 μm toabout 40 μm.
 15. The melt composition of claim 1, wherein the heatshrinkable foam structure is a foam tube.
 16. A melt composition for aheat-shrinkable foam structure, said composition comprising: (1) about80 to about 99.9% by weight of an ethylene/vinyl acetate copolymer basepolymer; (2) about 0.1 to about 10% by weight of a blowing agentcomprising: (a) a plurality of polymeric shells; and (b) at least oneheat-activated chemical compound, said heat-activated chemical compoundencapsulated in said polymeric shells; and (3) optionally, about 0% toabout 19.9% by weight of an optional filler.
 17. A method for making aheat-shrinkable polymer foam tube, comprising: (1) providing a meltcomposition, said melt composition comprising at least one base polymermaterial and a blowing agent, said base polymer material having a melttemperature and said blowing agent having an activation temperaturegreater than said melt temperature; (2) mixing said melt composition;(3) extruding said melt composition through a die to create an extrudedfoam tube having inner and outer surfaces; and (4) post processing saidextruded foam tube.
 18. The method of claim 17, wherein said step ofmixing is performed at a temperature greater than said melt temperatureof said base polymer material.
 19. The method of claim 17, wherein saidstep of extruding is performed at a temperature greater than or equal tosaid activation temperature of said blowing agent.
 20. The method ofclaim 17, wherein foaming of said melt composition occurs concurrentlywith said step of extruding said melt composition.
 21. The method ofclaim 17, wherein said step of post processing said extruded foam tubecomprises: (a) crosslinking said extruded foam tube; and (b) expandingsaid extruded foam tube.
 22. The method of claim 21, wherein said stepof post processing further comprises: (c) heating said extruded foamtube after crosslinking; (d) pressurizing the inner and outer surfacesof said extruded foam tube; and (e) cooling said extruded foam tube. 23.The method of claim 22, wherein said step of pressurizing the inner andouter surfaces of said extruded foam tube comprises subjecting the innerand outer surfaces of said extruded foam tube to a pressuredifferential.
 24. The method of claim 17, wherein said step of extrusionis performed with an annular die.
 25. The method of claim 21, whereinsaid step of crosslinking said extruded foam tube comprises irradiatingsaid foam tube.
 26. A heat shrinkable foamed polymer tube comprising afirst layer of an extruded foamed polymer tube, said first layer havinga void content and comprising (1) at least one base polymer; and (2) ablowing agent, said blowing agent comprising: (a) a plurality ofpolymeric shells; and (b) at least one heat-activated chemical compound,said heat-activated chemical compound encapsulated in said polymericshells.
 27. The heat shrinkable foamed polymer tube of claim 26; whereinthe first layer is an inner layer of said tube and said tube furthercomprises a second layer, which comprises an outer layer of saidextruded foamed polymer tube, said outer layer having a void content andcomprising (1) at least one base polymer; and (2) a blowing agent, saidblowing agent comprising: (a) a plurality of polymeric shells; and (b)at least one heat-activated chemical compound, said heat-activatedchemical compound encapsulated in said polymeric shells.
 28. The heatshrinkable foamed polymer tube of claim 27, wherein said base polymer ofsaid inner layer comprises a semicrystalline material.
 29. The heatshrinkable foamed polymer tube of claim 27, wherein said base polymer ofsaid outer layer comprises an elastomeric material.
 30. The heatshrinkable foamed polymer tube of claim 27, wherein the void content ofsaid outer layer is greater than the void content of said inner layer.31. The heat shrinkable foamed polymer tube of claim 27, wherein saidinner layer further comprises a tackifying filler material.
 32. The heatshrinkable foamed polymer tube of claim 31, wherein said tackifyingfiller is selected from the group consisting of novolak resins,partially polymerized resins, tall oil resin esters, and low molecularweight aromatic thermoplastic resins.
 33. The heat shrinkable foamedpolymer tube of claim 27, wherein the inner layer and the outer layerare co-extruded.
 34. The heat shrinkable foamed polymer tube of claim27, further comprising at least one intermediate layer between saidinner layer and said outer layer.
 35. The heat shrinkable foamed polymertube of claim 34, wherein said at least one intermediate layer comprisesa foamed polymer.